Bio-based base oils from fatty acids and biomass

ABSTRACT

Disclosed herein are lubricant compositions containing 75-99% by weight of a base oil that includes one or more branched aliphatic compounds having the following formula: R1R2HC—CH2—CHR3R4 (I) wherein R1 and R3 are independently selected from alkyl groups having 8 to 26 carbon atoms, and R2 and R4 are independently selected from the group consisting of H and alkyl groups having 5 to 7 carbon atoms, with a proviso that at least one of R2 and R4 is not hydrogen. The alkyl groups are substituted or unsubstituted, or branched or unbranched; R1 and R3 may be the same or different; and the total carbon content of the branched aliphatic compound of formula (I) is in the range of 26 to 66. The lubricant compositions also include an effective amount of one or more additives. Also, disclosed herein are processes for making such compositions and their uses in pharmaceutical and personal care products.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 62/772,672, filed Nov. 29, 2018, the entire disclosure of which isincorporated herein by reference for all purposes.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH

This invention was made with government support under DOE Grant No.DE-SC0001004 awarded by the Department of Energy. The government hascertain rights in the invention.

FIELD OF THE INVENTION

The present invention relates to lubricant compositions and inparticular to bio-based branched aliphatic compounds for use inlubricant compositions and base oils for pharmaceutical and personalcare product formulations, and methods of making such compounds.

BACKGROUND OF THE INVENTION

Lubricants are widely used in industrial machinery, automobiles,aviation machinery, refrigeration compressors, agricultural equipment,marine vessels and many other applications and represent an over $60billion global chemical enterprise. Base oils are key components(typically, 75-90 wt. %) of commercial formulated lubricants and accountfor up to 75% of lubricant cost. Base oils are also key components inthe formulations of personal care products, greases, and the like.According to the American Petroleum Institute (API), there are fivecategories of mineral base oils (Groups I-V). (Reference 3) Base oilsfrom Groups I through III are obtained by solvent-refining,distillation, or hydro-processing of petroleum. (Reference 4) Base oilsfrom Group IV have undergone chemical upgrading; for example, 1-decenefrom petroleum undergoes oligomerization to form poly-α-olefins (PAOs).(Reference 2) Finally, Group V includes all other oils. (Reference 3)ExxonMobil Basestocks 2018 Pulse Report suggests Group III+ oils willexperience the greatest increase in demand over the next 10 years (+4%increase) due to their high fuel efficiency and quality. (Reference 5)Nevertheless, their production is expensive and energy intensive,requires petroleum feedstocks, which contribute to greenhouse gasemissions, and harsh reaction conditions, especially when making GroupIV PAOs, whose synthesis requires corrosive catalysts (AlCl₃, BF₃, andHF). (References 4, 6) To mitigate these challenges, promising renewablealternatives from bio-derived feedstocks have gained momentum.(References 7-14) Bio-based feedstocks can result in a nearly “closedcarbon balance” through CO₂ capture during photosynthesis and haveunique functional groups that enable site-specific chemistries duringprocessing.

In one of the early attempts to make bio-based products, Corma andcoworkers produced n-tricosane, a linear alkane product with 23 carbons,from lauric acid, a fatty acid found in coconut and palm kernel oils.(Reference 11) This process involved ketonization of lauric acid to form12-tricosanone, containing 23 carbons, followed by itshydrodeoxygenation (HDO) to produce n-tricosane (58.2% selectivity) andC₁₀ through C₂₂ alkanes (13.9% selectivity total). Although the finalproduct would not be suitable as a Group III base oil (18 to 40 carbons)due to its poor viscosity and high melting point, the short-chainalkanes may be suitable for ultra-low sulfur diesel (ULSD) fuel. Despitethese obstacles, the strategy proposed by Corma and coworkers isappealing. The intermediate ketone, 12-tricosanone, can be obtained in89% yield by ketonization of lauric acid and is an ideal startingmaterial for lubricant synthesis because it contains a high number ofcarbons and can partake in carbon-carbon coupling reactions due to thepresence of a ketonic group.

Ketones are excellent platforms to incorporate branching due to theiracidic —CH group at the a carbon position. (References 3, 14, 17-20)Previously, Bell and coworkers performed multiple cross-ketonizationreactions, starting from short-chain length C₃-C₅ carboxylic acids,followed by HDO, to produce C₁₂-C₃₃ branched and cyclic alkane dieselfuels and lubricant base oils. (Reference 12) Wang and coworkersproduced C₂₃ bio-lubricant base oil with ˜50% yield from acetone andfurfural via successive aldol condensation and HDO steps. (Reference 10)While these routes use renewable feedstocks, e.g., carboxylic acid andacetone, which can be produced from sugar fermentation, andlignocellulosic biomass-derived furfural, they require multiple reactionsteps and extractions. This results in carbon loss, the need forexcessive amounts of solvent, and high production costs.

SUMMARY OF THE INVENTION

Accordingly, an object of the present invention is to provide novelstrategies to synthesize a highly branched bio-lubricant base oil infewer steps preferably using one or more bio-derived starting materials,for example a long chain ketone obtained from bio-derived fatty acids,and substituted or unsubstituted furfural, obtained from lignocellulosicbiomass. The synthesis of 12-tricosanone in high yield from lauric acidis discussed above. In the present invention, selective aldolcondensation of a furfural with a ketone such as 12-tricosanone isperformed followed by HDO to afford the final products, C₂₈ and C₃₃branched alkanes, having comparable viscosity to petroleum-derived GroupIII and Group IV base oils.

Thus, in an aspect of the invention, a lubricant composition isprovided, the lubricant composition comprising:

-   -   a. 75-99% by weight of a base oil comprising one or more        branched aliphatic compounds having the following formula:

R₁R₂HC—CH₂—CHR₃R₄  (I)

-   -   -   wherein:        -   (i) R₁ and R₃ are independently selected from alkyl groups            having 8 to 26 carbon atoms,        -   (ii) R₂ and R₄ are independently selected from the group            consisting of H and alkyl groups having 5 to 7 carbon atoms,            with a proviso that at least one of R₂ and R₄ is not            hydrogen,        -   wherein the alkyl groups are substituted or unsubstituted,            or branched or unbranched,        -   wherein R₁ and R₃ may be the same or different, and        -   wherein the total carbon content of the branched aliphatic            compound of formula (I) is in the range of 26 to 66; and

    -   b. an effective amount of one or more additives.

In an embodiment of the lubricant composition, at least one of the oneor more branched aliphatic compounds has a bio-based content in therange of 20 to 100%, according to ASTM-D6866.

In another embodiment of the lubricant composition, at least one of theone or more branched aliphatic compounds has one of the followingstructures:

In an embodiment of the lubricant composition, the base oil furthercomprises a minor amount (e.g., up to 25, up to 20, up to 15, up to 10or up to 5% by weight, based on the total weight of the lubricantcomposition) of one or more alkanes having a carbon content in the rangeof 1 to 25.

In yet another embodiment of the lubricant composition, the one or moreadditives are selected from the group consisting of antioxidants,stabilizers, detergents, dispersants, demulsifiers, antioxidants,anti-wear additives, pour point depressants, viscosity index modifiers,friction modifiers, anti-foam additives, defoaming agents, corrosioninhibitors, wetting agents, rust inhibitors, copper passivators, metaldeactivators, extreme pressure additives, and combinations thereof.

The lubricant composition as disclosed hereinabove may further compriseone or more co-base oils selected from the group consisting of API GroupI base oil, Group II base oil, Group III base oil, Group IV base oil,Group V base oil, gas-to-liquid (GTL) base oil, and combinationsthereof.

In an embodiment of the lubricant composition, at least one of the oneor more branched aliphatic compounds of formula (I) has a kinematicviscosity at 100° C. in the range of 2 to 100 cSt and a kinematicviscosity at 40° C. in the range of 6 to 100 cSt, as measured by ASTMD445. Additionally, at least one of the one or more branched aliphaticcompounds of formula (I) has a viscosity index, calculated from kineticviscosity at 100° C. and 40° C., in the range of 100 to 200, as measuredby ASTM D2270.

In an embodiment of the lubricant composition, at least one of the oneor more branched aliphatic compounds of formula (I) has a pour point inthe range of 2° C. to −160° C., as measured by ASTM D97; and anoxidation stability in the range of 150° C. to 300° C., as measured byASTM D6375.

In an aspect of the lubricant composition, the base oil has a kinematicviscosity of at least 3 cSt, as measured by ASTM D445 and a bio-basedcontent in the range of 30 to 100%, according to ASTM-D6866.

In another aspect, the lubricant composition is used in one or more ofindustrial machinery, automobiles, aviation machinery, refrigerationcompressors, agricultural equipment, marine vessels, agricultureequipment, medical equipment, hydropower production machinery, and foodprocessing equipment.

In an aspect, there is provided a composition comprising:

one or more branched aliphatic compounds having the following formula:

R₁R₂HC—CH₂—CHR₃R₄  (I)

wherein:

-   -   (i) R₁ and R₃ are independently selected from alkyl groups        having 8 to 26 carbon atoms,    -   (ii) R₂ and R₄ are independently selected from the group        consisting of H and alkyl groups having 5 to 7 carbon atoms,        with a proviso that at least one of R₂ and R₄ is not hydrogen,    -   wherein the alkyl groups are substituted or unsubstituted, or        branched or unbranched,    -   wherein R₁ and R₃ may be the same or different, and    -   wherein the total carbon content of the branched aliphatic        compound of formula (I) is in the range of 26 to 66; and

wherein the composition has a bio-based content in the range of 30 to100%, according to ASTM-D6866.

In another aspect, there is a method of making the compositioncomprising one or more branched aliphatic compounds having the formula(I), as disclosed hereinabove, the method comprising the steps of:

-   -   a) providing a first component comprising one or more of a        furfural or its derivative and a second component comprising a        ketone having the formula R₁R₃CO, wherein each R₁ and R₃ is        independently selected from the group consisting of alkyl groups        having 8 to 26 carbon atoms,        -   wherein at least one of the first component and the second            component is bio-derived from a renewable source;    -   b) condensing the first component with the second component in        the presence of a basic catalyst to form a condensed furan        compound (CF);

-   -   where R₅ is hydrogen, methyl, ethyl, or hydroxymethyl group.    -   c) hydrodeoxygenating the condensed furan compound (CF) in the        presence of a hydrodeoxygenation catalyst to obtain one or more        branched aliphatic compounds of formula (I).

In an embodiment of the method, the step of providing a second componentcomprises a ketone comprises ketonic decarboxylyzing one or more fattyacids from one or more natural oils or waste cooking oils.

In another embodiment of the method, the basic catalyst is selected fromthe group consisting of liquid bases (including inorganic liquid basesand organic liquid bases) and solid bases.

In yet another embodiment of the method, the hydrodeoxygenation catalystis a solid acid supported metal based catalyst, a physical mixture of ametal based catalyst, or a metal/metal oxide catalyst and preferablyPd/C, Pd/SiO₂ or Pt/C, with a solid acid. The solid acid supported metalbased catalyst can be selected from Ni/ZSM-5, Pd/ZSM-5, Pd/BEA, or aphysical mixture of a metal based catalyst with a solid acid, includingPd/C+ZSM-5, Pd/C+BEA, Pt/C+BEA, and preferably a supported metal-metaloxide catalyst such as Ir—ReO_(x)/SiO₂, Ir—MoO_(x)/SiO₂ or ¹M²MO/SiO₂,wherein ¹M=Ir, Ru, Ni, Co, Pd, Pt, or Rh and ²M=Re, Mo, W, Nb, Mn, V,Ce, Cr, Zn, Co, Y, or Al.

In an aspect of the invention, the composition prepared according to themethod as disclosed hereinabove, is used as a base oil in pharmaceuticaland personal care products.

In an aspect of the invention, a personal care composition is provided,the personal care composition comprising:

-   -   a) a base oil comprising the composition as disclosed        hereinabove; and    -   b) an effective amount of one or more additives selected from        the group consisting of pigments, fragrances, emulsifiers,        wetting agents, thickeners, emollients, rheology modifiers,        viscosity modifiers, gelling agents, antiperspirant agents,        deodorant actives, fatty acid salts, film formers,        anti-oxidants, humectants, opacifiers, monohydric alcohols,        polyhydric alcohols, fatty alcohols, preservatives, pH        modifiers, moisturizers, skin conditioners, stabilizing agents,        proteins, skin lightening agents, topical exfoliants,        antioxidants, retinoids, refractive index enhancers,        photo-stability enhancers, SPF improvers, UV blockers, and        water.

In an embodiment, the personal care composition further comprises anactive ingredient selected from the group consisting of antibiotic,antiseptic, antifungal, corticosteroid, and anti-acne agent.

In an aspect of the invention, a pharmaceutical composition is provided,the pharmaceutical composition comprising:

-   -   a. a base oil comprising the composition as disclosed        hereinabove;    -   b. an effective amount of one or more pharmaceutically active        ingredients; and    -   c. optionally, one or more pharmaceutically acceptable        excipients.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated in and constitute apart of this specification, illustrate various embodiments or aspects ofthe invention, and together with the written description, serve toexplain certain principles of the invention.

FIG. 1 shows a renewable approach to produce bio-lubricant base oilcomprising branched aliphatic compounds. Base-catalyzed aldolcondensation (AC) of furfural and 12-tricosanone is performed to form aC₃₃ furan intermediate, along with a small fraction of a C₂₈intermediate, followed by their hydrodeoxygenation (HDO) over anIr—ReO_(x)/SiO₂ catalyst to produce base oils containing C₃₃ branchedalkane as the major component.

FIG. 2 shows conversion of 12-tricosanone to C₃₃-CF (“C₃₃ CondensedFuran”), a condensed furan compound, as a function of solvents. Reactionconditions: 0.227 g furfural and 0.1 g 12-tricosanone (mole ratio=8:1),80° C., 24 hrs. Studies performed with no co-solvent, cyclohexane, anddioxane contained 100 μL of 1 M NaOH. Methanol and water studiescontained 1 M NaOH.

FIG. 3 shows the yields of C₂₈ and C₃₃ furan intermediates obtained fromthe reaction of 12-tricosanone with furfural. Reaction conditions: 1 mol(0.1 g) tricosanone, 8 mol (0.227 g) furfural, 80° C. Cyclohexane,dioxane and no co-solvent studies were performed with 100 μL of 1 MNaOH. Methanol and water contained 0.2 g NaOH in 5 mL solvent, 24 h.

FIG. 4 shows (a) the GC spectra of the aldol condensation (AC) productobtained from a reaction of furfural (0.45 g) and 12-tricosanone (0.10g). Potential isomers are highlighted in the panels on the right; (b)the GC spectra of product obtained after HDO of aldol condensationproduct. AC products are C₂₈ and C₃₃ furan isomers (0.40 g). HDOproducts are primarily chiral isomers of the C₂₈ and C₃₃ alkanes.Eicosane (0.10 g) is used the internal standard to quantify products,post-reaction, in (a) and (b). m/z was obtained separately, using GC-MS.Reaction conditions: 8 hrs, 80° C., 5 mL methanol, 16:1 mol ratiofurfural:tricosanone, 1 M NaOH.

FIG. 5 shows the mass fragments of products after (a) aldol condensationand (b) hydrodeoxygenation reactions using HRMS-LIFDI. Solvents for bothreactions were removed prior to analysis, and samples were prepared indichloromethane (1 mg/mL). m/z was obtained from Liquid Injection FieldDesorption/Ionization-Mass Spectrometry (LIFDI-MS). Reaction conditions:16 h, 180° C., 5 MPa H₂, 20 mL cyclohexane, ˜0.1 g furans, 0.05 gIr—ReO_(x)/SiO₂ (experimental). 1 mg/mL in dichloromethane, catalystremoved (LIFDI-MS).

FIG. 6 shows the ¹H NMR spectrum obtained to characterize an aldolcondensation product. Sample was prepared in CDCl₃ (1 mg/mL). Thepredominant product is the C₃₃ furan, followed by the C₂₈ furan, andtheir isomers. The highlighted bonds in C₃₃H₅₀O₃ are referencing thehydrogen atoms.

FIG. 7 shows the ¹³C NMR spectrum obtained to characterize an aldolcondensation product. Sample was prepared in CDCl₃ (1 mg/mL). Thehighlighted bonds in C₃₃H₅₀O₃ are referencing the carbon atoms.

FIG. 8 shows the ¹H NMR spectrum obtained to characterize anhydrodeoxygenation product. Sample was prepared in CDCl₃ (1 mg/mL). Thehighlighted bonds in C₃₃H₆₈ are referencing the hydrogen atoms. Highmolecular weight oxygenates are likely present, as indicated by thechemical shifts at ˜3.7 ppm.

FIG. 9 shows the ¹H NMR spectrum obtained to characterize ahydrodeoxygenation product. Sample was prepared in CDCl₃ (1 mg/mL). Thehighlighted bonds in C₃₃H₆₈ are referencing the hydrogen atoms. Highmolecular weight oxygenates are likely present, as indicated by thechemical shifts at ˜3.7 ppm.

FIG. 10 shows the ¹³C NMR spectrum obtained to characterize ahydrodeoxygenation product. Sample was prepared in CDCl₃ (1 mg/mL). Thehighlighted bonds in C₃₃H₆₈ are referencing the carbon atoms. Chemicalshifts above 60 ppm may correspond to the carbons associated with theunidentified oxygenates.

FIG. 11A shows yields of furan intermediates from the reaction of12-tricosanone (0.10 g) with varying amounts of furfural at 80° C. andwith 1 M NaOH in methanol (5 mL) for 8 hrs. Error bars correspond tomean±standard error of the mean (SEM) of three independent reactions.

FIG. 11B shows the product distribution after performing HDO on thealdol condensation furan intermediates shown in FIG. 11A with a moleratio of furfural:12-tricosanone: 16:1. HDO reaction conditions: 16 h,180° C., 5 MPa, H₂, 20 mL cyclohexane, 0.4 g C₂₈ and C₃₃ furans, 0.15 gIr—ReO_(x)/SiO₂, 2 replicates.

FIG. 12 shows (a) Carbon-carbon (C—C) cracking in the tertiary carbonpositions of the C₃₃ alkane to produce alkane byproducts. (b) C—Ccracking in secondary carbon positions; the dashed line is anotherpossible route to obtain the C₁₄ alkane instead of the C₁₅ alkane.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the term “biomass-derived” is used interchangeably with“biologically-derived”, “bio-derived” or “bio-based” and refers tocompounds that are obtained from renewable resources such as plants andcontain either only or substantially renewable carbon, and no or a veryminimal amount fossil fuel-based or petroleum-based carbon.

Assessment of the content of renewably based carbon in a material can beperformed through standard test methods. Using radiocarbon and isotoperatio mass spectrometry analysis, the bio-based content of materials canbe determined, using ASTM-D6866-18 (a standard method established byASTM International, formally known as the American Society for Testingand Materials).

As used herein, the “bio-based content” is determined in accordance withASTM-D6866-18 and is built on the same concepts as radiocarbon dating,but without use of the age equations. The analysis is performed byderiving a ratio of the amount of radiocarbon (¹⁴C) in an unknown sampleto that of a modern reference standard. The ratio is reported as apercentage with the units “pMC” (percent modern carbon) with modern orpresent defined as 1950. If the material being analyzed is a mixture ofpresent day radiocarbon and fossil carbon (containing no radiocarbon),then the pMC value obtained correlates directly to the amount of biomassmaterial present in the sample.

Combining fossil carbon with present day carbon into a material willresult in a dilution of the present day pMC content. By presuming 107.5pMC represents present day biomass materials and 0 pMC representspetroleum derivatives, the measured pMC value for that material willreflect the proportions of the two component types. A material derived100% from present day plants/trees would give a radiocarbon signaturenear 107.5 pMC. If that material was diluted with 50% petroleumderivatives, it would give a radiocarbon signature near 54 pMC.

A bio-mass content result is derived by assigning 100% equal to 107.5pMC and 0% equal to 0 pMC. In this regard, a sample measuring 99 pMCwill give an equivalent bio-based content result of 93%.

Assessment of the biodegradability of a material, such as of branchedaliphatic compounds of formula (I), base oils, or compositions such aslubricant compositions and personal care compositions of the presentdisclosure, can be performed through standard test methods, such asthose developed by the Organization for Economic Cooperation andDevelopment (OECD), the Coordinating European Council (CEC), and theAmerican Society for Testing and Materials (ASTM), such as, OECD 301B(the Modified Strum test), ASTM D-5864-18, and CEC L-33-A-934. Both OECD301B and ASTM D-5864-18 measure ready biodegradability, defined as theconversion of 60% of the material to CO₂ within a ten day windowfollowing the onset of biodegradation, which must occur within 28 daysof test initiation. In contrast, the CEC method tests the overallbiodegradability of hydrocarbon compounds and requires 80% or greaterbiodegradability as measured by the infrared absorbance of extractablelipophilic compounds.

As used herein, the terms “lubricant”, “lubricant composition”, and“lubricant base oil” refer to any substance used to reduce friction byproviding a protective film between two moving surfaces. In general, alubricant exhibits one or more characteristics, such as, high viscosityindex, high boiling point, thermal stability, oxidation stability, lowpour point, corrosion prevention capability and low surface tension.

As used herein, a “condensation” reaction refers to a chemical reactionin which two molecules combine to form a larger molecule while producinga small molecule, such as H₂O, as a byproduct.

As used herein, a “hydrogenation” reaction refers to a chemical reactionbetween molecular hydrogen and another compound, typically, in thepresence of a catalyst to reduce or saturate organic compounds.

As used herein, a “hydrodeoxygenation” or “HDO” reaction refers to achemical reaction whereby a carbon-oxygen bond is cleaved or undergoeslysis (cleavage of a C—O bond) by hydrogen, typically in the presence ofa catalyst. “HDO” is a process for removing oxygen from a compound.

The term “kinematic viscosity” is used herein to refer to a fluid'sinherent resistance to flow when no external force other than gravity isacting on the fluid. “Kinematic viscosity” is measured as the ratio ofabsolute (or dynamic) viscosity to density.

The term “pour point” as used herein refers to the temperature belowwhich a liquid loses its flow characteristics.

Process of Making a Composition Comprising One or More BranchedAliphatic Compounds Represented by Formula (I)

The invention disclosed herein relates to a composition comprising oneor more branched aliphatic compounds as represented by the formula (I)from one or more bio-derived reactants, the process of making suchcompositions and their use as base oils in lubricant compositions,personal care compositions and pharmaceutical compositions.

In an aspect of the invention, the composition comprises one or morebranched aliphatic compounds having the following formula:

R₁R₂HC—CH₂—CHR₃R₄  (I)

wherein the composition has a bio-based content in the range of 30 to100%, according to ASTM-D6866-18.

In the branched aliphatic compounds of formula (I), R₁ and R₃ areindependently selected from alkyl groups having 8 to 26 carbon atoms, R₂and R₄ are independently selected from the group consisting of H andalkyl groups having 5 to 7 carbon atoms, with a proviso that at leastone of R₂ and R₄ is not hydrogen, and the total carbon content of theone or more branched aliphatic compounds of formula (I) is in the rangeof 26 to 66 (meaning that the compound contains a total of from 26 to 66carbon atoms).

As used herein the alkyl groups can be substituted or unsubstituted, orbranched or unbranched (linear) or a combination thereof. Suitableexamples of alkyl groups include, but are not limited to, C₅-C₂₆ alkylgroups, including, but not limited to, pentyl, hexyl, heptyl, octyl,nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl,hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosanyl.

In an embodiment, R₁ and R₃ may be the same. In another embodiment, R₁and R₃ may be different. In yet another embodiment, R₁ and R₃ areindependently chosen from alkyl groups having 8 to 26 carbon atoms,preferably from acyclic unbranched alkyl groups having 8-26 carbonatoms, and most preferably from acyclic unbranched alkyl groups having8-16 carbon atoms, provided that in total the one or more branchedaliphatic compounds of formula (I) contain from 26 to 66 carbon atoms.

Suitable examples of R₁ and R₃ include, but are not limited to, C₈-C₂₆alkyl groups including, but not limited to, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl,heptadecyl, octadecyl, nonadecyl, and icosanyl.

In an embodiment, one of R₂ and R₄ is hydrogen. In another embodiment,R₂ and R₄ may be independently chosen from among alkyl groups having 5-7carbon atoms, or 5-6 carbon atoms, provided that in total the branchedaliphatic compound contains from 26 to 66 carbon atoms. Suitableexamples of R₂ and R₄ include, but are not limited to, hydrogen, pentyl,hexyl, and heptyl.

In an embodiment, at least one of R₁ and R₃ is a branched alkyl group,having one or more branches. The one or more branches can have anysuitable number of carbon atoms, with at least one of the brancheshaving 1-18 carbon atoms, and preferably 1-10 carbon atoms.

Suitable examples of branched alkyl groups, having one or more branchesinclude, but are not limited to, 2-methylpentane, 3-ethylpentane, and4-ethylhexane.

In an aspect, the one or more branched aliphatic compounds of formula(I), have one of the following structures:

where R₁, R₂, R₃, and R₄, are defined as hereinabove, provided that intotal the branched aliphatic compound contains 26 to 66 carbon atoms.

In some embodiments, the composition also comprises a minor amount ofone or more alkanes having a carbon content in the range of 1 to 25, or5 to 20, or 5 to 15.

In an aspect, there is provided a process of making a compositioncomprising one or more branched aliphatic compounds as represented byformula (I). The process includes providing a first component comprisingone or more of a furfural or its derivative and a second componentcomprising a ketone having the formula R₁R₃CO, wherein each R₁ and R₃ isindependently selected from the group consisting of alkyl groups having8 to 26 carbon atoms and where at least one of the first component andthe second component is bio-derived from a renewable source.

Furfural is one of the oldest renewable chemicals. Furfural or itsderivatives can be produced by removing water from or dehydratingfive-carbon sugars such as xylose and arabinose. These pentose sugarsare commonly obtained from the hemicellulose fraction of biomass wasteslike cornstalks, corncobs, oat, wheat bran, and sawdust, and the husksof peanuts and oats.

In an embodiment, the step of providing a second component comprising aketone comprises ketonic decarboxylyzing one or more fatty acidsobtained from one or more natural oils or waste cooking oils. The fattyacids may, for example, be obtained by splitting (hydrolyzing)triglycerides found in such oils. The mixtures of fatty acids therebytypically obtained may be used as mixtures in the ketonicdecarboxylation reaction or may be fractionated or purified to producethe fatty acid(s) employed to provide the ketone(s) comprising thesecond component. Suitable examples of fatty acids include, but are notlimited to saturated C₁₀-C₂₄ fatty acids such as lauric acid, palmiticacid and stearic acid. In some embodiments, the fatty acid is anunsaturated fatty acid, including, but not limited to, oleic acid,myristoleic acid, palmitoleic acid, linoleic acid, and sapienic acid.Such fatty acids may be derived from any suitable natural cooking oilsincluding, but not limited, to coconut oil, palm oil, rapeseed oil,vegetable oil, corn oil, peanut oil, olive oil, canola oil, andsunflower oil. The fatty acids may also be derived from any wastecooking oils of one or more natural cooking oils and/or animal fats. Thesynthesis of ketones of different carbon length via selectivehydrogenation of fatty acids from natural oils or WCO is known in theart.

The process of making a composition comprising one or more branchedaliphatic compounds of formula (I) further includes condensing the firstcomponent with the second component in the presence of a basic catalystto form a condensed furan compound (CF). Any suitable basic catalyst canbe used. In an embodiment, the basic catalyst is chosen from liquidbases, including inorganic liquid bases and organic liquid bases. Forexample, the liquid base may be a solution of a base in a suitablesolvent. In another embodiment, the basic catalyst is chosen from amongsolid bases.

Exemplary inorganic liquid bases include, but are not limited to,aqueous solutions of sodium hydroxide, potassium hydroxide, calciumhydroxide, and barium hydroxide. Exemplary organic liquid bases include,but are not limited to, pyridine, methylamine, and imidazole. Exemplarysolid bases include, but are not limited to, alumina oxide, titaniumoxide, lanthanum oxide, hydrotalcite, magnesium oxide, calcium oxide,and potassium cyanide.

Exemplary CF compounds include, but are not limited to,11,13-di((tetrahydrofuran-2-yl)methyl)tricos-11,13-dien-12-one and11-di((tetrahydrofuran-2-yl)methyl)tricos-11-dien-12-one.

The first component comprising one or more of a furfural or a derivativethereof and a second component comprising a ketone having the formulaR₁R₃CO can be provided in any suitable amount. In the context of thepresent invention, “a derivative thereof” (i.e., a furfural derivative)means a furfural compound substituted with one or more substituents suchas alkyl (e.g., methyl) or hydroxyalkyl (e.g., hydroxymethyl) groups.Any suitable furfural derivative may be used including but not limitedto methyl furfural and hydroxymethyl furfural.

In an embodiment, a molar ratio of the first component to the secondcomponent can be from 1:1 to 25:1 or from 6:1 to 25:1 or from 7:1 to20:1 or from 8:1 to 16:1. The condensation reaction can be carried outfor any suitable amount of time such as from 1 second to 24 hours.

In an embodiment, the condensation reaction is carried out in thepresence of one or more suitable solvents. Any suitable solvent,preferably capable of dissolving reactants and/or catalyst can be used.In an embodiment, the solvent is a polar, protic solvent, such asmethanol, ethanol, isopropanol, butanol, and pentanol.

The condensation reaction can carried out at any suitable temperature,such as in the range of 25 to 200° C. or 40 to 150° C. or 65 to 85° C.for any suitable amount of time, such as from 1 second to 24 hours or 3to 20 hours or 5 to 12 hours. In an embodiment, the condensationreaction can be carried out at 80° C. for 8 hours.

In an embodiment, the process comprises a step of purification of acondensed furan compound prior to a hydrodeoxygenation step. Anysuitable method can be used to purify condensed furan compound, such as,for example removal of methanol and unconverted furfural from acondensation reaction product using rotary evaporation. The resultingproduct can be washed and neutralized with a dilute solution ofhydrochloric acid (1 M) and extracted with dichloromethane.Dichloromethane can then be removed by rotary evaporation prior to thehydrodeoxygenation step.

In an embodiment, the process of making a composition comprising one ormore branched aliphatic compounds of formula (I) may also includehydrodeoxygenating the condensed furan compound (CF) in the presence ofa hydrodeoxygenation catalyst and molecular hydrogen to obtain one ormore branched aliphatic compounds of formula (I).

Any suitable hydrodeoxygenation (HDO) catalyst may be used, such as asolid acid supported metal based catalyst or a physical mixture of ametal based catalyst, or a metal/metal oxide catalyst, and preferablyPd/C, Pd/SiO₂ and Pt/C, with a solid acid. Suitable solid acid supportedmetal based catalysts includes, but are not limited to, Ni/ZSM-5,Pd/ZSM-5, Pd/BEA; a physical mixture of a metal based catalyst with asolid acid, which includes but is not limited to, Pd/C+ZSM-5, Pd/C+BEA,Pt/C+BEA, and preferably supported metal-metal oxide catalysts such asIr—ReO_(x)/SiO₂, Ir—MoO_(x)/SiO₂ or ¹M²MO/SiO₂, where ¹M can be chosenfrom among Ir, Ru, Ni, Co, Pd, Pt, Rh and ²M can be chosen from amongRe, Mo, W, Nb, Mn, V, Ce, Cr, Zn, Co, Y, Al.

The HDO reaction can be carried out at any suitable temperature, such asin the range of 100 to 300° C. or 125 to 250° C. or 150 to 210° C. forany suitable amount of time, such as from 1 to 30 hours or 5 to 25 hoursor 10 to 22 hours in the presence of hydrogen gas at 0.5 to 15 MPa or 1to 12 MPa or 2 to 9 MPa. In an embodiment, the condensation reaction canbe carried out at 180° C. for about 18 hours at a hydrogen pressure of 5MPa at 500 rpm. The process can further include a step forpurification/fractionation of hydrodeoxygenation products to removelower molecular weight C₁-C₂₅ minor products, before use as a lubricantcomposition.

In an embodiment, the process further comprises reducing the catalystfor the HDO reaction prior to the step of HDO reaction. The catalystpre-reduction can be carried out at temperature and pressure conditionssimilar to those used in the HDO reaction, but for a shorter amount oftime and preferably in the presence of an organic solvent. Any suitableC₂-C₈ alkane can be used as a solvent. In an embodiment, the solvent forpre-reduction of catalyst is cyclohexane. In an embodiment, thepre-reduction of catalyst is carried out in cyclohexane as a solvent at200° C. and at a hydrogen pressure of 5 MPa for 1 hour with stirring at240 rpm.

Exemplary branched aliphatic compounds of formula (I) include, but arenot limited to, 11,13-dipentyltricosane and 11-pentyltricosane.

In an aspect of the invention, the one or more branched aliphaticcompounds of formula (I) have a bio-based content in the range of 20% to100%, e.g., at least 20%, at least 30%, at least 35%, at least 40%, atleast 45%, at least 50%, at least 55%, at least 60%, at least 65%, atleast 70%, at least 75%, at least 80%, at least 85%, at least 90%, atleast 95%, at least 96%, at least 97%, at least 98%, at least 99%, or100%; preferably 30 to 100%; and most preferably 50 to 100%, asdetermined according to ASTM-D6866-18.

In another aspect, a lubricant composition includes 75-99% by weight ofa base oil comprising one or more branched aliphatic compounds offormula (I), in accordance with various embodiments of the presentinvention, as disclosed hereinabove, and an effective amount of one ormore additives. According to various embodiments, one or more branchedaliphatic compounds of formula (I) may comprise at least 20%, at least30%, at least 40%, at least 50%, at least 60%, at least 70%, at least80%, at least 90%, at least 95%, at least 99% or even 100% by weight ofthe base oil.

In an embodiment, the lubricant base oil, as disclosed hereinabove isderived from lauric acid-derived tricosanone and furfural. Lauric acidis primarily found in coconut oil and palm kernel oil. It should benoted that while palm oil comes from the palm fruit, palm kernel oilcomes from the palm seed. Both coconut oil and palm kernel oil containapproximately 50 wt. % lauric acid. Therefore, the coconut oil and palmkernel oil are used interchangeably in industry given their similarcomposition. Additionally, lauric acid-derived lubricant base oils arepromising for multiple reasons, including, but not limited to:

Climate change will have little effect on coconut oil and palm kerneloil production. Although cyclones are a growing environmental concernthat could impact coconut oil production, but it should not impactlauric acid production due to palm trees being located in regions lesslikely to experience extreme weather and the effects of climate change.

Copra production requires much less fertilizer as compared to soya beanand rapeseed, which draw large quantities of nitrogen from the soil.Prior art estimates that rapeseed requires 100 kg of nitrogen per ton ofoil produced, compared to 25 kg of nitrogen per ton of palm oilproduced. Additionally, copra production uses virtually no fossil fuels,as fertilizers are rarely, if ever, applied. Therefore, with theimportant exception of increasing transportation costs, copra industrieswill not be affected by rising energy costs.

Coconut trees and oil palm trees have long lifespans, approximately60-80 years and 30 years, respectively. At the end of a tree's lifetime,the leftover timber can be used to produce additional products (andrevenue). Veneer plywood from copra trees is a profitable venture. Soyabeans and rapeseed do not have this functionality.

In an embodiment of the lubricant composition, the base oil comprisingat least one of the one or more branched aliphatic compounds of formula(I) has a bio-based content in the range of 20 to 100%, e.g., at least20%, at least 30%, at least 35%, at least 40%, at least 45%, at least50%, at least 55%, at least 60%, at least 65%, at least 70%, at least75%, at least 80%, at least 85%, at least 90%, at least 95%, at least96%, at least 97%, at least 98%, at least 99%, or 100%; preferably 30 to100%; more preferably 40 to 100%; and most preferably 50 to 100%, asdetermined according to ASTM-D6866-18.

In an embodiment of the lubricant composition, at least one of the oneor more branched aliphatic compounds has one of the followingstructures:

where R₁, R₂, R₃, and R₄, are defined as hereinabove, provided that intotal the branched aliphatic compound contains 26 to 66 carbon atoms.

In another embodiment, the base oil further comprises a minor amount ofone or more alkanes having a carbon content in the range of 1 to 25, or5 to 20, or 5 to 15. In an embodiment, where the base oil is derivedfrom furfural and lauric acid, the composition comprises minor amount ofone or more alkanes having a carbon content in the range of 10 to 15.While intending not to be bound by any theory, it is believed that suchalkanes are products of C—C cracking in the tertiary and secondarycarbon positions, such as shown in FIG. 12.

In an embodiment of the lubricant composition, the one or more lubricantadditives may be selected from among antioxidants, stabilizers,detergents, dispersants, demulsifiers, antioxidants, anti-wearadditives, pour point depressants, viscosity index modifiers, frictionmodifiers, anti-foam additives, defoaming agents, corrosion inhibitors,wetting agents, rust inhibitors, copper passivators, metal deactivators,extreme pressure additives, and combinations thereof. Any of suchlubricant additives may be used in an amount effective to impart one ormore desired properties or characteristics to the lubricant composition.Typically, effective concentrations of such lubricant additives will besimilar to those utilized in conventional lubricant compositions,although in certain cases lower or higher concentrations may be neededor desired due to the different characteristics of the base oilscomprised of one or more branched aliphatic compounds of formula (I)which are present in the lubricant compositions of the presentinvention. In certain cases, individual lubricant additives are includedin the lubricant composition at only a few ppm, but in other cases anindividual lubricant additive is employed in an amount of at least 10ppm, at least 50 ppm, at least 100 ppm, at least 250 ppm, at least 500ppm, at least 750 ppm, at least 1000 ppm, at least 2000 ppm, at least3000 ppm, at least 4000 ppm, at least 5000 ppm, or even higher (e.g., atleast 1% by weight), depending upon the type of lubricant additive andthe effect desired to be achieved by the inclusion of the lubricantadditive. Generally speaking, however, the total amount of lubricantadditive does not exceed 25% by weight based on the total weight of thelubricant composition. According to other embodiments, the lubricantcomposition comprises not more than 20%, not more than 15%, not morethan 10% or not more than 5% by weight in total of lubricantadditive(s), based on the total weight of the lubricant composition.

In another embodiment, the lubricant composition may further include oneor more co-base oils (i.e., base oils other than the base oil comprisedof one or more branched aliphatic compounds of formula (I)). Forexample, the co-base oil may be selected from the group consisting ofAmerican Petroleum Institute (API) Group I base oil, Group II base oil,Group III base oil, Group IV base oil, Group V base oil, gas-to-liquid(GTL) base oil, and combinations thereof.

According to certain embodiments, the lubricant composition is comprisedof a) from 75-99% by weight of a base oil comprised of one or morebranched aliphatic compounds of formula (I) and b) from 1-25% by weightin total of one or more additional components selected from the groupconsisting of lubricant additives and co-base oils, the total of a) andb) equaling 100%.

In yet another embodiment of the lubricant composition, at least one ofthe one or more branched aliphatic compounds of formula (I) has akinematic viscosity in the range of 2 to 100 centistokes (cSt) at 100°C., preferably 2-50 cSt, most preferably 2-30 cSt and in the range of 6to 100 cSt at 40° C., preferably 6-50 cSt, most preferably 6-30 cSt, asmeasured by ASTM D445, such that a viscosity index calculated fromkinetic viscosity at 100° C. and 40° C., is in the range of 100 to 200,as measured by ASTM D2270, and the base oil has a kinematic viscosity ofat least 3 cSt, as measured by ASTM D445.

In one embodiment of the lubricant composition, at least one of the oneor more branched aliphatic compounds of formula (I) has a pour point inthe range of 2° C. to −160° C., or 2° C. to −120° C., or 2° C. to −80°C., or 2° C. to −65° C., as measured by ASTM D97.

In certain embodiments of the lubricant composition, at least one of theone or more branched aliphatic compounds of formula (I) has an oxidationstability in the range of 150° C. to 300° C., preferably 170° C. to 280°C., and most preferably 170° C. to 250° C., as measured by ASTM D6375.

In an aspect of the invention, the lubricant composition may be used inone or more of industrial machinery, automobiles, aviation machinery,refrigeration compressors, agricultural equipment, marine vessels,agriculture equipment, medical equipment, hydropower productionmachinery, and/or food processing equipment.

In another aspect of the invention, the base oil comprising one or morebranched aliphatic compounds of formula (I), in accordance with variousembodiments of the present invention, as disclosed hereinabove, may beused in one or more of industrial machinery, automobiles, aviationmachinery, refrigeration compressors, agricultural equipment, marinevessels, agriculture equipment, medical equipment, hydropower productionmachinery, and/or food processing equipment. In another embodiment, thebase oil comprising one or more branched aliphatic compounds of formula(I), in accordance with various embodiments of the present invention, asdisclosed hereinabove, may be used in pharmaceutical formulations andpersonal care product formulations, e,g, sunscreen, lotion, creams,cosmetics, and the like.

According to still further embodiments, a method is provided of reducingat least one of friction or wear between a first surface and a secondsurface, wherein the method comprises lubricating at least one of thefirst surface and the second surface with a base oil or a lubricantcomposition comprising one or more branched aliphatic compounds offormula (I) in accordance with the present invention. The first surfaceand the second surface may be the same as or different from each otherand may be constructed of any suitable material, including for examplemetal, coated metal, plastic, and/or ceramic.

Also provided by the present invention is a method of lowering thecoefficient of friction of a substrate surface, wherein the methodcomprises applying a coating of a base oil or lubricant compositioncomprised of one or more branched aliphatic compounds of formula (I) tothe substrate surface. The substrate may be comprised of any suitablematerial such as metal, coated metal, plastic and/or ceramic.

In yet another aspect, a personal care composition is provided, thepersonal care composition including a base oil comprising one or morebranched aliphatic compounds of formula (I), in accordance with variousembodiments of the present invention, as disclosed hereinabove, and aneffective amount of one or more additives. Any suitable additive couldbe used, including, but not limited to, pigments, fragrances,emulsifiers, wetting agents, thickeners, emollients, rheology modifiers,viscosity modifiers, gelling agents, antiperspirant agents, deodorantactives, fatty acid salts, film formers, anti-oxidants, humectants,opacifiers, monohydric alcohols, polyhydric alcohols, fatty alcohols,preservatives, pH modifiers, moisturizers, skin conditioners,stabilizing agents, proteins, skin lightening agents, topicalexfoliants, antioxidants, retinoids, refractive index enhancers,photo-stability enhancers, SPF improvers, UV blockers, and water. Inanother embodiment, the personal care composition may further comprisean active ingredient selected from the group consisting of antibiotic,antiseptic, antifungal, corticosteroid, and anti-acne agent. Thepersonal care composition of the present disclosure may be used in anysuitable application including, but not limited to, cosmetics,sunscreens, lotions, creams, antiperspirants, deodorants, and medicatedointments, creams, and oils.

In still another aspect, a pharmaceutical composition is provided, thepharmaceutical composition including a base oil comprising one or morebranched aliphatic compounds of formula (I), in accordance with variousembodiments of the present invention, as disclosed hereinabove, aneffective amount of one or more pharmaceutically active ingredients,and, optionally, one or more excipients (other than base oils comprisingone or more branched aliphatic compounds of formula (I)). Any suitablepharmaceutically active ingredient(s) could be used, including inparticular oil-soluble drugs, such as anti-inflammatory agents,antibiotics, antifungals, acne treatment agents, scabies/lice treatmentagents, corticosteroids and analgesics. The pharmaceutical compositioncould, for example, take the form of a cream, lotion, foam, gel,ointment, emulsion (including both water-in-oil and oil-in-wateremulsions) or paste and may be a topical preparation, oral formulationor injectable formulation. The base oil comprising one or more branchedaliphatic compounds of formula (I) may function, for example, as acarrier, vehicle, solubilizing excipient or filler (such as in softgelatin capsules and the like).

Thus, the present invention provides a viable route to obtain a branchedalkane based bio-lubricant base oil in fewer steps from long-chainketone, such as 12-tricosanone, which can be obtained from fatty acid,and an aldehyde such as furfural, which can be obtained fromlignocellulosic biomass. This approach involved aldol condensationfollowed by HDO. The strategy to synthesize renewable base oilsdescribed in the present disclosure could be a potential stepping-stoneto replace petroleum-derived base oils, which in turn can reducegreenhouse gas emissions. Additionally, low temperature processingcompared to the current refinery processing (cracking and distillationfor synthetic and mineral base oils), and the use of sustainablefeedstock with abundant supply and possible biodegradability could makethis process and products competitive and adaptive to the existingmarket place.

Aspects of the Invention

Certain illustrative, non-limiting aspects of the invention may besummarized as follows:

-   -   Aspect 1. A lubricant composition comprising:        -   a. 75-99% by weight of a base oil comprising one or more            branched aliphatic compounds having the following formula:

R₁R₂HC—CH₂—CHR₃R₄  (I)

-   -   -   -   wherein:            -   (i) R₁ and R₃ are independently selected from alkyl                groups having 8 to 26 carbon atoms,            -   (ii) R₂ and R₄ are independently selected from the group                consisting of H and alkyl groups having 5 to 7 carbon                atoms, with a proviso that at least one of R₂ and R₄ is                not hydrogen,            -   wherein the alkyl groups are substituted or                unsubstituted, or branched or unbranched,            -   wherein R₁ and R₃ may be the same or different, and            -   wherein the total carbon content of the branched                aliphatic compound of formula (I) is in the range of 26                to 66; and

        -   b. an effective amount of one or more additives.

    -   Aspect 2. The lubricant composition according to Aspect 1,        wherein at least one of the one or more branched aliphatic        compounds has a bio-based content in the range of 20 to 100%,        according to ASTM-D6866.

    -   Aspect 3. The lubricant composition according to either of        Aspects 1 or 2, wherein at least one of the one or more branched        aliphatic compounds has one of the following structures:

-   -   Aspect 4. The lubricant composition according to any of Aspects        1-3, wherein the base oil further comprises a minor amount of        one or more alkanes having a carbon content in the range of 1 to        25.    -   Aspect 5. The lubricant composition according to any of Aspects        1-4, wherein the one or more additives are selected from the        group consisting of antioxidants, stabilizers, detergents,        dispersants, demulsifiers, antioxidants, anti-wear additives,        pour point depressants, viscosity index modifiers, friction        modifiers, anti-foam additives, defoaming agents, corrosion        inhibitors, wetting agents, rust inhibitors, copper passivators,        metal deactivators, extreme pressure additives, and combinations        thereof.    -   Aspect 6. The lubricant composition according to any of the        Aspects 1-5, further comprising one or more co-base oils        selected from the group consisting of API Group I base oil,        Group II base oil, Group III base oil, Group IV base oil, Group        V base oil, gas-to-liquid (GTL) base oil, and combinations        thereof.    -   Aspect 7. The lubricant composition according to any of Aspects        1-6, wherein at least one of the one or more branched aliphatic        compounds of formula (I) has a kinematic viscosity at 100° C. in        the range of 2 to 100 cSt, as measured by ASTM D445.    -   Aspect 8. The lubricant composition according to any of Aspects        1-6, wherein at least one of the one or more branched aliphatic        compounds of formula (I) has a kinematic viscosity at 40° C. in        the range of 6 to 100 cSt, as measured by ASTM D445.    -   Aspect 9. The lubricant composition according to any of Aspects        1-8, wherein at least one of the one or more branched aliphatic        compounds of formula (I) has a viscosity index, calculated from        kinetic viscosity at 100° C. and 40° C., in the range of 100 to        200, as measured by ASTM D2270.    -   Aspect 10. The lubricant composition according to any of Aspects        1-9, wherein at least one of the one or more branched aliphatic        compounds of formula (I) has a pour point in the range of 2° C.        to −120° C., as measured by ASTM D97.    -   Aspect 11. The lubricant composition according to any of Aspects        1-10, wherein at least one of the one or more branched aliphatic        compounds of formula (I) has an oxidation stability in the range        of 150° C. to 300° C., as measured by ASTM D6375.    -   Aspect 12. The lubricant composition according to any of Aspects        1-11, wherein the base oil has a kinematic viscosity of at least        3 cSt, as measured by ASTM D445.    -   Aspect 13. The lubricant composition according to any of Aspects        1-12, wherein the base oil has a bio-based content in the range        of 30 to 100%, according to ASTM-D6866.    -   Aspect 14. Use of the lubricant composition according to any of        Aspects 1-13, in one or more of industrial machinery,        automobiles, aviation machinery, refrigeration compressors,        agricultural equipment, marine vessels, agriculture equipment,        medical equipment, hydropower production machinery, and food        processing equipment.    -   Aspect 15. A composition comprising:        -   one or more branched aliphatic compounds having the            following formula:

R₁R₂HC—CH₂—CHR₃R₄  (I)

-   -   -   -   wherein:            -   (i) R₁ and R₃ are independently selected from alkyl                groups having 8 to 26 carbon atoms,            -   (ii) R₂ and R₄ are independently selected from the group                consisting of H and alkyl groups having 5 to 7 carbon                atoms, with a proviso that at least one of R₂ and R₄ is                not hydrogen,            -   wherein the alkyl groups are substituted or                unsubstituted, or branched or unbranched,            -   wherein R₁ and R₃ may be the same or different, and            -   wherein the total carbon content of the branched                aliphatic compound of formula (I) is in the range of 26                to 66; and            -   wherein the composition has a bio-based content in the                range of 30 to 100%, according to ASTM-D6866.

    -   Aspect 16. A method of making the composition of Aspect 15, the        method comprising the steps of:        -   a) providing a first component comprising one or more of a            furfural or its derivative and a second component comprising            a ketone having the formula R₁R₃CO, wherein each R₁ and R₃            is independently selected from the group consisting of alkyl            groups having 8 to 26 carbon atoms, wherein at least one of            the first component and the second component is bio-derived            from a renewable source;        -   b) condensing the first component with the second component            in the presence of a basic catalyst to form at least one            condensed furan compound (CF) selected from the group            consisting of:

-   -   -   where R₅ is hydrogen, methyl, ethyl, or hydroxymethyl group;            and        -   c) hydrodeoxygenating the at least one condensed furan            compound (CF) in the presence of a hydrodeoxygenation            catalyst to obtain one or more branched aliphatic compounds            of formula (I).

    -   Aspect 17. The method according to Aspect 16, wherein the step        of providing a second component comprising a ketone comprises        ketonic decarboxylyzing one or more fatty acids from one or more        natural oils or waste cooking oils.

    -   Aspect 18. The method according to either Aspect 16 or Aspect        17, wherein the basic catalyst is selected from the group        consisting of liquid bases (including inorganic liquid bases and        organic liquid bases) and solid bases.

    -   Aspect 19. The method according to any of Aspects 16-18, wherein        the hydrodeoxygenation catalyst is a solid acid supported metal        based catalyst, a physical mixture of a metal based catalyst, or        a metal/metal oxide catalyst and preferably Pd/C, Pd/SiO₂ or        Pt/C, with a solid acid.

    -   Aspect 20. The method according to Aspect 19, wherein the        hydrodeoxygenation catalyst is a solid acid supported metal        based catalyst selected from Ni/ZSM-5, Pd/ZSM-5, Pd/BEA, or a        physical mixture of a metal based catalyst with a solid acid,        including Pd/C+ZSM-5, Pd/C+BEA, Pt/C+BEA, and preferably a        supported metal-metal oxide catalyst such as Ir—ReO_(x)/SiO₂,        Ir—MoO_(x)/SiO₂ or ¹M²MO/SiO₂, wherein ¹M=Ir, Ru, Ni, Co, Pd,        Pt, or Rh and ²M=Re, Mo, W, Nb, Mn, V, Ce, Cr, Zn, Co, Y, or Al.

    -   Aspect 21. Use of the composition prepared according to any of        Aspects 16-20, as a base oil in pharmaceutical and personal care        products.

    -   Aspect 22. A personal care composition comprising:        -   a. a base oil comprising the composition of Aspect 15; and        -   b. an effective amount of one or more additives selected            from the group consisting of pigments, fragrances,            emulsifiers, wetting agents, thickeners, emollients,            rheology modifiers, viscosity modifiers, gelling agents,            antiperspirant agents, deodorant actives, fatty acid salts,            film formers, anti-oxidants, humectants, opacifiers,            monohydric alcohols, polyhydric alcohols, fatty alcohols,            preservatives, pH modifiers, moisturizers, skin            conditioners, stabilizing agents, proteins, skin lightening            agents, topical exfoliants, antioxidants, retinoids,            refractive index enhancers, photo-stability enhancers, SPF            improvers, UV blockers, and water.

    -   Aspect 23. The personal care composition of Aspect 22, further        comprising an active ingredient selected from the group        consisting of antibiotic, antiseptic, antifungal,        corticosteroid, and anti-acne agent.

    -   Aspect 24. A pharmaceutical composition comprising:        -   a. a base oil comprising the composition of Aspect 15;        -   b. an effective amount of one or more pharmaceutically            active ingredients; and        -   c. optionally, one or more pharmaceutically acceptable            excipients.

As used herein, when an amount, concentration, or other value orparameter is given as either a range, preferred range, or a list ofupper preferable values and lower preferable values, this is to beunderstood as specifically disclosing all ranges formed from any pair ofany upper range limit or preferred value and any lower range limit orpreferred value, regardless of whether ranges are separately disclosed.Where a range of numerical values is recited herein, unless otherwisestated, the range is intended to include the endpoints thereof, and allintegers and fractions within the range. It is not intended that thescope of the invention be limited to the specific values recited whendefining a range.

The term “about” refers to the variation in the numerical value of ameasurement, e.g., temperature, weight, percentage, length,concentration, and the like, due to typical error rates of the deviceused to obtain that measure. In one embodiment, the term “about” meanswithin 5% of the reported numerical value.

As used herein, the singular form of a word includes the plural, andvice versa, unless the context clearly dictates otherwise. Thus, thereferences “a”, “an”, and “the” are generally inclusive of the pluralsof the respective terms. Likewise the terms “include”, “including” and“or” should all be construed to be inclusive, unless such a constructionis clearly prohibited from the context. Similarly, the term “examples,”particularly when followed by a listing of terms, is merely exemplaryand illustrative and should not be deemed to be exclusive orcomprehensive.

The term “comprising” is intended to include embodiments encompassed bythe terms “consisting essentially of” and “consisting of”. Similarly,the term “consisting essentially of” is intended to include embodimentsencompassed by the term “consisting of”.

Within this specification, embodiments have been described in a waywhich enables a clear and concise specification to be written, but it isintended and will be appreciated that embodiments may be variouslycombined or separated without departing from the invention. For example,it will be appreciated that all preferred features described herein areapplicable to all aspects of the invention described herein.

In some embodiments, the invention herein can be construed as excludingany element or process step that does not materially affect the basicand novel characteristics of the compounds for use as a lubricant baseoil, lubricant base oil compositions based on such compounds and processfor making such compounds. Additionally, in some embodiments, theinvention can be construed as excluding any element or process step notspecified herein.

Although the invention is illustrated and described herein withreference to specific embodiments, the invention is not intended to belimited to the details shown. Rather, various modifications may be madein the details within the scope and range of equivalents of the claimsand without departing from the invention.

EXAMPLES

Examples of the present invention will now be described. The technicalscope of the present invention is not limited to the examples describedbelow.

Abbreviations

The meaning of abbreviations is as follows: “cm” means centimeter(s),“g” means gram(s), “h” or “hr” means hour(s), “HPLC” means high pressureliquid chromatography, “m” means meter(s), “min” means minute(s), “mL”means milliliter(s), “mm” means millimeter(s), “MPa” meansmegapascal(s), “psi” means pound(s) per square inch, “rpm” meansrevolutions per minute, “wt %” means weight percent(age).

Example 1. General Materials and Methods

Materials

Furfural and 12-tricosanone were purchased from Tokyo Chemical IndustryCo. Methanol (≥99.8%), sodium hydroxide pellets, hydrochloric acid (36.5to 38.0%), and cyclohexane (99.9%) were purchased from FisherScientific. Eicosane (99%) and hydrogen hexachloroiridate hydrate(99.98%, metal basis) were purchased from Sigma-Aldrich. Ammoniumperrhenate (VII) (99.999% metals basis) was purchased from Alfa Aesar.Fuji Silysia Chemical Ltd. G6 (BET surface area, 535 m²/g) suppliedsilica gel.

Catalyst Preparation

The Ir—ReO_(x)/SiO₂(Ir 4 wt % loading, Re/Ir=2, molar) catalyst wasprepared by a sequential impregnation method.^([21]) First, Ir/SiO₂ wasprepared by impregnating Ir on SiO₂ (Fuji Silysia G-6) using an aqueoussolution of hydrogen hexachloroiridate hydrate. Next, the solvent wasevaporated at 75° C. on a hotplate (IKA) and dried at 110° C. for 12 hrsin an oven (Fisher Scientific). The resulting Ir/SiO₂ was impregnatedwith ReO_(x) using an aqueous solution of ammonium perrhenate(VII). Thecatalyst was calcined in a crucible in air at 500° C. for 3 hrs at a 10°C./min temperature ramp. The reported metal loadings in the catalyst arebased on the theoretical amount of metals used for impregnation. Thecatalyst was used in powder form with a granule size of <400 mesh. BETsurface area measurements were performed on a Micromeritics ASAP 2020Accelerated Surface Area and Porosimetry instrument at the AdvancedMaterials Characterization Laboratory at the University of Delaware. Themeasured BET surface area of Ir—ReO_(x)/SiO₂ was 368.6 m²/g.

Reaction Procedures

Process of Making a Condensed Furan Compound (CF) by Aldol CondensationReaction

All reactions were conducted in 10 mL glass vials (Sigma-Aldrich) heatedin an aluminum heating block with controlled stirring (FisherScientific). In a standard reaction, the reactants, furfural (4.68 mmol,0.45 g) and 12-tricosanone (0.295 mmol, 0.10 g), were combined with thesolvent, methanol (5 mL), and catalyst, sodium hydroxide (1 M, 0.20 g).The catalyst concentration was selected from a prior report (Reference10). Temperature and stirring rate were maintained at 80° C. and 400rpm, respectively. After reaction for the set time, the reaction vialswere removed from the heating block and cooled to room temperature.Methanol and unconverted furfural were removed by rotatory evaporation(Buchi). The products were washed and neutralized with a dilute solutionof hydrochloric acid (1 M) and extracted with dichloromethane (20 mL).Dichloromethane was removed by rotary evaporation prior to HDO. Theproducts formed by aldol condensation were solids at room temperature.

Process of Making a Branched Alkane Compound (BA) by Hydrodeoxygenation(HDO) Reaction

HDO reactions of aldol condensation products were conducted in a 50 mLParr reactor with an inserted Teflon liner and a magnetic bar. Thecatalyst, Ir—ReO_(x)/SiO₂ (0.15 g), and solvent, cyclohexane (5 mL),were added to the reactor for catalyst pre-reduction. The reactor wassealed with a fitted reactor head that contained a thermocouple, arupture disk, a pressure gauge, and a gas release valve. The mixture washeated at 200° C. and 5 MPa H₂ for 1 hr at 240 rpm. Upon pre-reduction,the reactor was cooled to room temperature and H₂ was released. Next,the aldol condensation products (0.40 g) were mixed with cyclohexane (15mL) and added to the reactor. The reactor head was immediately closed,purged with 1 MPa H₂ three times, and pressurized to 5 MPa H₂. Thereaction occurred over 18 hrs at 180° C. and with continuous stirring at500 rpm. The heating time to reach the set temperature was approximately25 min and was not included in the total reaction time. Upon completion,the reactor was immediately transferred to a water bath. The catalystwas separated from the solution by centrifugation.

Analysis of Products

The products were analyzed using a gas chromatograph (GC, Agilent7890A), equipped with an HP-1 column and a flame ionization detector.Products were quantified using eicosane (C₂₀) as the internal standard(0.10 g). The products were identified by a GC (Agilent 7890B) massspectrometer (MS, Agilent 5977A with a triple-axis detector), equippedwith a DB-5 column. High resolution mass spectrometry-liquid injectionfield desorption ionization (HRMS-LIFDI, Waters GCT Premier) data wereobtained from the Mass Spectrometry Facility at the University ofDelaware. ¹H and ¹³C nuclear magnetic resonance spectroscopy (NMR,Bruker AV400, CDCl₃ solvent) were also used to identify the productsfrom aldol condensation and HDO.

The conversion and the yield of all products from aldol condensation andHDO reactions were calculated on carbon basis using the followingequations:

${{Conversion}\mspace{14mu}\lbrack\%\rbrack} = {\frac{{{mol}\mspace{14mu}{of}\mspace{14mu}{initial}\mspace{14mu}{reactant}} - {{mol}\mspace{14mu}{of}\mspace{14mu}{unreacted}\mspace{14mu}{reactant}}}{{mole}\mspace{14mu}{of}\mspace{14mu}{initial}\mspace{14mu}{reactant}} \times 100}$${{Yield}\mspace{14mu}{of}\mspace{11mu}{detected}\mspace{14mu}{{products}\mspace{14mu}\left\lbrack {\%\text{-}C} \right\rbrack}} = {\frac{{mol}_{product} \times C\mspace{14mu}{atoms}\mspace{14mu}{in}\mspace{14mu}{product}}{{mol}\mspace{14mu}{of}\mspace{14mu}{total}\mspace{14mu} C\mspace{14mu}{atoms}\mspace{14mu}{of}\mspace{14mu}{initial}\mspace{14mu}{reactants}} \times 100}$

Lubricant Base Oil Properties Measurements

Cyclohexane and lower boiling point alkanes (<C₆) in the products wereremoved by rotary evaporation prior to viscosity measurements.

The lubricant properties of the final HDO products were evaluatedaccording to the American Society for Testing and Materials (ASTM)methods.

The kinematic viscosities at 100° C. and 40° C. (KV100 and KV40) weredetermined following the ASTM D445 method.

The viscosity index (VI) was calculated using the KV100 and KV40,following the ASTM D2270 method.

An extra low charge semi-micro viscometer (Cannon, size 150, calibratedmodel #: 9722-H62) apparatus was used for all measurements. The samplecharge volume was 300 μL. To demonstrate the accuracy of this method,the viscosity of a Cannon® N35 Standard and an Exxon Mobil SpectraSynPlus™ PAO-4 (Group IV) were measured and found that as-measuredviscosities were in agreement with the reported values, as shown belowin Table 1.

TABLE 1 Viscosities measured by the micro-viscometer compared to thereported viscosities. KV100 (cSt) KV40 (cSt) Base Oil Measured ReportedMeasured Reported Cannon ® N35 Standard 6.17 5.56 36.04 32.82 ExxonMobil SpectraSyn 4.15 4.10 17.13 18.40 Plus ™ PAO-4 (group IV)Viscosity Index (VI) from ASTM D2270 can be calculated as follows:

${VI} = {\frac{10^{N} - 1}{0.00715} + 100}$$N = \frac{{\log(H)} - {\log(U)}}{\log(Y)}$

whereH is kinematic viscosity at 40° C. of an oil of 100 viscosity indexhaving the same kinematic viscosity at 100° C. as the oil whoseviscosity index is to be calculated, mm²/s; obtained using Table 1 inASTM D2270,U is kinematic viscosity at 40° C., andY is kinematic viscosity at 100° C.

Example 2. Synthesis of Condensed Furan Compound, C₃₃-CF by AldolCondensation of Furfural and 12-Tricosanone Using Different Solvents

All reactions were catalyzed by 1 M NaOH (unless otherwise specified),and the reaction temperature was 80° C. for all experiments to ensure12-tricosanone (melting point=68° C.) was a liquid at reactiontemperature.

FIG. 2 shows the yield of products and conversion of 12-tricosanone indifferent solvents. Previous works have shown that aldol condensationmay occur with^([10]) or without a solvent. (Reference 22) As shown inFIG. 2, conversion of 12-tricosanone was low (<25%) and no C₂₈ or C₃₃furan intermediates were detected without a solvent, indicating theobserved conversion of 12-tricosanone was likely due to itsoligomerization with itself and/or furfural. Rio et al. suggested thatcarboxyl and hydroxyl groups may promote oligomerization to form highmolecular weight organic compounds found in oils and source rocks.(Reference 23) These oligomers, however, are difficult to detect byconventional GC columns due to their high molecular weights (>C₄₀).(References 21, 24) Without wishing to be bound by any particulartheory, it is believed that the carboxyl and hydroxyl groups in12-tricosanone and furfural promote the formation of high molecularweight, solid oligomeric species called humins, whose characterizationis reported in prior work. (Reference 25)

Since having no solvent led to low conversion of 12-tricosanone, nextdifferent solvents were screened as a function of their polarity. Asshown in FIG. 2, non-polar, aprotic solvents, such as cyclohexane anddioxane, resulted in very low yield of condensation product, which islikely due to their poor ability to dissolve the reactants and catalyst,combined with their inability to donate protons. In contrast, as shownin FIG. 2, a polar, protic solvent, such as methanol resulted in thehighest conversion of 12-tricosanone, likely due to methanol's abilityto dissolve the reactants and catalyst. Given the propensity ofmethanol, water was also tested, but it resulted in no yield of product.The observed conversion of 12-tricosanone with water as the solvent, asshown in FIG. 2 is likely due to the formation of humins. Water was mostlikely ineffective because it is a product of aldol condensation, andwhen used as a solvent, it shifts equilibrium towards the reactants,according to Le Chatelier's principle. Therefore, subsequent aldolcondensation were performed in methanol.

Example 3. Synthesis of Condensed Furan Compound, C₃₃-CF by AldolCondensation of Furfural and 12-Tricosanone with Different Mole Ratiosand Reaction Times

Next, experiments were conducted as a function of reaction time and feedratio to achieve high yields in desired condensation product, i.e., C₃₃furan intermediate. Initially, reactions were carried out for 24 hrs andwith mole ratios of furfural:12-tricosanone ranging from 1:1 to 16:1, asshown in FIG. 3. GC-MS detected two fragments with a mass to chargeratio (m/z) of 416 and nine fragments with an m/z of 464, whichcorrespond to geometric isomers of the C₂₈ and C₃₃ furans, respectively,as shown in FIG. 4a . All isomers corresponding to the same m/z fragmentas one product were considered for yield calculation. Additionalanalysis by HRMS-LIFDI shown in FIGS. 5a and 5b and ¹H and ¹³C NMRspectra shown in FIGS. 6 and 7, were consistent with the C₂₈ and C₃₃products identified from GC-MS.

As shown in FIG. 11A, the product distribution, i.e. yield of C₃₃ versusC₂₈, could be tuned by changing the feed ratio of reactants, where highamounts of furfural favored the C₃₃ furan (Y_(C) ₃₃ _(furan)=64.8% whenfurfural:12-tricosanone is 8:1). The yields of total detected C₂₈ andC₃₃ furans are lower than the 12-tricosanone conversion, which could bedue to the formation of humins. Higher selectivity to desiredcondensation products was achieved by decreasing the reaction time from24 hrs, shown in FIGS. 3 to 8 hrs, shown in FIG. 11A. A maximum 94.3%yield of branched furan intermediates containing C₃₃ as the majorproduct (Y_(C) ₂₈ _(furan)=14.8% and Y_(C) ₃₃ _(furan)=79.5%, FIG. 11A)is obtained for 8 hrs and at furfural to 12-tricosanone molar ratio of16:1. Excess furfural can be recycled upon separation using rotaryevaporation. Higher feed ratio beyond 16:1, such as 25:1 resulted in aslight decrease in the yield of C₃₃ furan and the overall yield, asshown in FIG. 11A.

Example 4. Synthesis of Branched Alkane C₃₃-BA by Hydrodeoxygenation ofC₃₃-CF

Aldol condensation product, after neutralizing and removing methanol andany unconverted furfural, was dissolved in cyclohexane and transferredto the Parr reactor for hydrodeoxygenation (HDO) using the proceduredescribed hereinabove in Example 1.

HDO of C₂₈ and C₃₃ condensed furan compounds mixture (Y_(C) ₂₈_(furan)=14.8% and Y_(C) ₃₃ _(furan)=79.5%) over Ir—ReO_(x)/SiO₂ at 180°C. and 5 MPa H₂ in cyclohexane for 18 hrs yielded 61.4% of totallubricant-ranged branched alkanes (C₂₈ and C₃₃). FIG. 11B shows that themajor products are C₃₃ (Y_(C) ₃₃ =50.5%) and C₂₈ (Y_(C) ₂₈ =10.9%)alkanes, followed by C₁₅, C₁₄, C₁₃ and C₁₀ alkanes (Y_(combine)<11%),which likely result from carbon-carbon (C—C) cracking in the tertiaryand secondary carbons of the C₃₃ and C₂₈ alkanes, as shown in FIG. 11.In the present synthesis of branched alkanes via HDO, C₅ alkane islikely to form via C—C cracking as shown in FIG. 12, but it was notquantified because of difficulty arising from the solvent, cyclohexane,forming C ₁-C₆ alkanes during pre-reduction of the catalyst and duringthe HDO reaction. Thus, alkanes with less than six carbons were notquantified. In addition to C₅ alkane, gaseous C₁-C₄ alkanes could alsoform from the substrates in the HDO step to account for some of thecarbon loss, but gas phase products were not quantified in this work.Furthermore, coke formation on the catalyst and unidentified oxygenatedintermediates may contribute to the remaining carbon loss. Cokeformation is not expected to hinder recycling the catalyst, as Liu etal. have demonstrated that upon re-calcination, the catalyst can beregenerated with similar activity to that of the fresh catalyst.(Reference 26) GC-MS and HRMS-LIFDI detected mass fragments expected forC₂₈ and C₃₃ alkane products, as shown in FIGS. 5 and 6 respectively.Additionally, the NMR spectra were congruent with that expected for theC₃₃ alkane product, as shown in FIGS. 9 and 10.

Example 5. Properties of C₃₃-BA Based Base Oils of the Present Inventionand Commercial Formulated Lubricants

The bio-lubricant base oil having branched alkane (C₃₃-BA) compounds,such as obtained in Example 4, is a viscous liquid at room temperatureand even at low temperature, ˜3° C., while n-tricosane, containing 23carbons and produced by HDO of 12-tricosanone, is solid. (Reference 11)This suggests the addition of branches on linear alkanes by method inaccordance with the present invention can significantly improve the lowtemperature flow property. The viscous properties of as-synthesized baseoil are determined by extra-low charge, micro-viscosity measurements andare compared to those of Phillips 66 Ultra-S 3™ (Group III) and ExxonMobil SpectraSyn Plus™ PAO-3.6 (Group IV) base oils.

When considering lubricant base oils, at high temperatures (100° C.), anoil's viscosity (KV100) should be high to create a thick hydrodynamicfilm between surfaces. Upon decreasing temperature (40° C.), an oil'sviscosity (KV40) should be low, or less resistant to flow, to promotefluidity. The VI, calculated using the KV100 and KV40 values, measuresviscosity stability of a fluid as a function of temperature. MaximizingVI ensures that the oil's viscosity varies as little as possible withtemperature.

Table 2 shows that KV100, KV40, and VI of the C₃₃-BA based base oil arecomparable to commercial Group III and Group IV base oils. The VI of theC₃₃-BA based base oil is 115, which is higher than 100, suggesting theC₃₃-BA based base oil of the present invention has high quality.(Reference 6)

TABLE 2 Properties of C₃₃-BA based base oil (Y_(C) ₃₃ = 50.5% and Y_(C)₂₈ = 10.9%) compared to Group III and Group IV commercial lubricants.KV100* KV40* Base Oil (cSt) (cSt) VI^(†) C₃₃-BA based Base Oil 3.4314.37 115 Phillips 66 Ultra-S 3 ™ (Group III)^(‡) 3.26 13.20 116 ExxonMobil SpectraSyn Plus ™ PAO-3.6 3.6 15.4 120 (Group IV)^(‡) *KV40 andKV100 are kinematic viscosities at 40° C. and 100° C., respectively(ASTM D445). ^(†)VI calculated from KV40 and KV100 (ASTM D2270). ^(‡)Theproperties of commercial products were obtained from the productspecifications datasheet disclosed by the manufacturers.

Thus, as disclosed herein above, the present invention provides a viableroute to obtain a branched alkane based bio-lubricant base oil in fewersteps from long-chain ketone, such as 12-tricosanone, which can beobtained from fatty acid, and an aldehyde such as furfural, which can beobtained from lignocellulosic biomass. This approach involved aldolcondensation followed by HDO. Aldol condensation of 12-tricosanone andfurfural at 16:1 molar ratio resulted in maximum 93.5% yield of branchedC₂₈ and C₃₃ furan intermediates in 8 hrs. C₃₃ furan intermediate was themajor product, 79.5%, with balance being C₂₈ furan intermediate.Subsequent HDO of aldol condensation product over an Ir—ReO_(x)/SiO₂(Re/Ir molar ratio=2) yielded 72% total alkanes, in whichlubricant-ranged branched alkanes, C₂₈ and C₃₃, were 61%. Small amounts(11%) of low carbon alkanes (>C₁₀) were detected. Micro-viscositymeasurements indicated that the base oil of the present invention hasviscous properties comparable to petroleum-derived Group III and IVoils. The strategy to synthesize renewable base oils described in thepresent disclosure could be a potential stepping-stone to replacepetroleum-derived base oils, which in turn can reduce greenhouse gasemissions.

REFERENCES AND NOTES

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1. A lubricant composition comprising: a. 75-99% by weight of a base oilcomprising one or more branched aliphatic compounds having the followingformula:R₁R₂HC—CH₂—CHR₃R₄  (I) wherein: (i) R₁ and R₃ are independently selectedfrom alkyl groups having 8 to 26 carbon atoms, (ii) R₂ and R₄ areindependently selected from the group consisting of H and alkyl groupshaving 5 to 7 carbon atoms, with a proviso that at least one of R₂ andR₄ is not hydrogen, wherein the alkyl groups are substituted orunsubstituted, or branched or unbranched, wherein R₁ and R₃ may be thesame or different, and wherein the total carbon content of the branchedaliphatic compound of formula (I) is in the range of 26 to 66; and b. aneffective amount of one or more additives.
 2. The lubricant compositionaccording to claim 1, wherein at least one of the one or more branchedaliphatic compounds has a bio-based content in the range of 20 to 100%,according to ASTM-D6866.
 3. The lubricant composition according to claim1, wherein at least one of the one or more branched aliphatic compoundshas one of the following structures:


4. The lubricant composition according to claim 1, wherein the base oilfurther comprises a minor amount of one or more alkanes having a carboncontent in the range of 1 to
 25. 5. The lubricant composition accordingto claim 1, wherein the one or more additives are selected from thegroup consisting of antioxidants, stabilizers, detergents, dispersants,demulsifiers, antioxidants, anti-wear additives, pour point depressants,viscosity index modifiers, friction modifiers, anti-foam additives,defoaming agents, corrosion inhibitors, wetting agents, rust inhibitors,copper passivators, metal deactivators, extreme pressure additives, andcombinations thereof.
 6. The lubricant composition according to claim 1,further comprising one or more co-base oils selected from the groupconsisting of API Group I base oil, Group II base oil, Group III baseoil, Group IV base oil, Group V base oil, gas-to-liquid (GTL) base oil,and combinations thereof.
 7. The lubricant composition according toclaim 1, wherein at least one of the one or more branched aliphaticcompounds of formula (I) has a kinematic viscosity at 100° C. in therange of 2 to 100 cSt, as measured by ASTM D445.
 8. The lubricantcomposition according to claim 1, wherein at least one of the one ormore branched aliphatic compounds of formula (I) has a kinematicviscosity at 40° C. in the range of 6 to 100 cSt, as measured by ASTMD445.
 9. The lubricant composition according to claim 1, wherein atleast one of the one or more branched aliphatic compounds of formula (I)has a viscosity index, calculated from kinetic viscosity at 100° C. and40° C., in the range of 100 to 200, as measured by ASTM D2270.
 10. Thelubricant composition according to claim 1, wherein at least one of theone or more branched aliphatic compounds of formula (I) has a pour pointin the range of 2° C. to −160° C., as measured by ASTM D97.
 11. Thelubricant composition according to claim 1, wherein at least one of theone or more branched aliphatic compounds of formula (I) has an oxidationstability in the range of 150° C. to 300° C., as measured by ASTM D6375.12. The lubricant composition according to claim 1, wherein the base oilhas a kinematic viscosity of at least 3 cSt, as measured by ASTM D445.13. The lubricant composition according to claim 1, wherein the base oilhas a bio-based content in the range of 30 to 100%, according toASTM-D6866.
 14. A method comprising providing the lubricant compositionaccording to claim 1, and using it for lubricating industrial machinery,an automobile, aviation machinery, a refrigeration compressor,agricultural equipment, a marine vessel, agriculture equipment, medicalequipment, hydropower production machinery, and food processingequipment.
 15. A composition comprising: one or more branched aliphaticcompounds having the following formula:R₁R₂HC—CH₂—CHR₃R₄  (I) wherein: R₁ and R₃ are independently selectedfrom alkyl groups having 8 to 26 carbon atoms, R₂ and R₄ areindependently selected from the group consisting of H and alkyl groupshaving 5 to 7 carbon atoms, with a proviso that at least one of R₂ andR₄ is not hydrogen, wherein the alkyl groups are substituted orunsubstituted, or branched or unbranched, wherein R₁ and R₃ may be thesame or different, and wherein the total carbon content of the branchedaliphatic compound of formula (I) is in the range of 26 to 66; andwherein the composition has a bio-based content in the range of 30 to100%, according to ASTM-D6866.
 16. A method of making the composition ofclaim 15, the method comprising the steps of: a) providing a firstcomponent comprising one or more of a furfural or its derivative and asecond component comprising a ketone having the formula R₁R₃CO, whereineach R₁ and R₃ is independently selected from the group consisting ofalkyl groups having 8 to 26 carbon atoms, wherein at least one of thefirst component and the second component is bio-derived from a renewablesource; b) condensing the first component with the second component inthe presence of a basic catalyst to form at least one condensed furancompound (CF) selected from the group consisting of:

where R₅ is hydrogen, methyl, ethyl, or hydroxymethyl; and c)hydrodeoxygenating the at least one condensed furan compound (CF) in thepresence of a hydrodeoxygenation catalyst to obtain one or more branchedaliphatic compounds of formula (I).
 17. The method according to claim16, wherein the step of providing a second component comprising a ketonecomprises ketonic decarboxylyzing one or more fatty acids from one ormore natural oils or waste cooking oils.
 18. The method according toclaim 16, wherein the basic catalyst is selected from the groupconsisting of liquid bases (including inorganic liquid bases and organicliquid bases) and solid bases.
 19. The method according to claim 16,wherein the hydrodeoxygenation catalyst is a solid acid supported metalbased catalyst, a physical mixture of a metal based catalyst, or ametal/metal oxide catalyst and preferably Pd/C, Pd/SiO₂ or Pt/C, with asolid acid.
 20. The method according to claim 19, wherein thehydrodeoxygenation catalyst is a solid acid supported metal basedcatalyst selected from Ni/ZSM-5, Pd/ZSM-5, Pd/BEA, or a physical mixtureof a metal based catalyst with a solid acid, including Pd/C+ZSM-5,Pd/C+BEA, Pt/C+BEA, and preferably a supported metal-metal oxidecatalyst such as Ir—ReO_(x)/SiO₂, Ir—MoO_(x)/SiO₂ or ¹M²MO/SiO₂, wherein¹M=Ir, Ru, Ni, Co, Pd, Pt, or Rh and ²M=Re, Mo, W, Nb, Mn, V, Ce, Cr,Zn, Co, Y, or Al.
 21. A method comprising preparing the compositionaccording to claim 16, and using it as a base oil in a pharmaceutical orpersonal care product.
 22. A personal care composition comprising: abase oil comprising the composition of claim 15; and an effective amountof one or more additives selected from the group consisting of pigments,fragrances, emulsifiers, wetting agents, thickeners, emollients,rheology modifiers, viscosity modifiers, gelling agents, antiperspirantagents, deodorant actives, fatty acid salts, film formers,anti-oxidants, humectants, opacifiers, monohydric alcohols, polyhydricalcohols, fatty alcohols, preservatives, pH modifiers, moisturizers,skin conditioners, stabilizing agents, proteins, skin lightening agents,topical exfoliants, antioxidants, retinoids, refractive index enhancers,photo-stability enhancers, SPF improvers, UV blockers, and water. 23.The personal care composition of claim 22, further comprising an activeingredient selected from the group consisting of antibiotics,antiseptics, antifungals, corticosteroids, and anti-acne agents.
 24. Apharmaceutical composition comprising: a base oil comprising thecomposition of claim 15; an effective amount of one or morepharmaceutically active ingredients; and optionally, one or morepharmaceutically acceptable excipients.